A unique photoinduced change in the molecular ordering of a photochromic diarylethene derivative having amide groups was investigated at the liquid/highly oriented pyrolytic graphite (HOPG) interface by scanning tunneling microscopy (STM). Ordering of the diarylethene was stabilized by the hydrogen-bonded network of amide groups. The open- and the closed isomers formed characteristic stripe-patterned orderings; a different hydrogen-bonding network was formed in each case. In situ UV irradiation resulted in the exclusive formation of a third molecular ordering gamma that is composed of the photoirreversible annulated isomer. No photoisomerized molecule was detected in the 2-D orderings, i.e., the open-ring isomer in the ordering of the closed-ring isomer and vice versa, despite the similarity in their molecular structures.